Absorbent composition

ABSTRACT

This invention provides an absorbent composition comprising a reactant product of (1) amines or amides; (2) carbon disulfide, or carbonyl sulfide; (3) polyvalent metal ions; and, (4) a waterdispersable reactive polymeric material. A water-soluble silicate may be present as an optional material during the reaction. The reaction is carried out in an alkaline water solution or dispersion, and the above noted absorbent composition then precipitates. The resulting absorbent composition may be used as an ion exchange medium; to form lakes by absorption of dyes soluble or dispersable in water or water-immiscible solvents; to absorb from water solutions or dispersions of toxic or otherwise objectionable materials such as chromates, lead or mercury salts, etc.; to absorb dye intermediates, which when absorbed may be further reacted to form dyes which remain on the composition of this invention; to coat paper and facilitating ink absorption on paper; to manufacture pigments which blend readily in oleophylic vehicles, as well as in hydrophylic vehicles.

United States Patent Remer 51 May 13, 1975 ABSORBENT COMPOSITION [75]Inventor: Robert K. Remer, Evanston, Ill.

[73] Assignee: Hull-Smith Chemicals, Inc., Des

Plaines, Ill.

[22] Filed: June 29, 1973 [21] Appl. No.: 374,929

Related US. Application Data I [63] Continuation of Ser. No. lZ9,602,March 30, 197i,

abandoned.

[52] US. Cl. 252/1; 8/85; 252/428; 252/438; 260/21 R; 260/785 T [51]Int. Cl C09k 3/00 [58] Field of Search 260/785 T; 252/428, 438, 252/1[56] References Cited FOREIGN PATENTS OR APPLICATIONS l.029,055 5/1966United Kingdom OTHER PUBLICATIONS Kuzkin et al., Tsvetnye Metally, Vol.33, No. 2, pp. 17 to 20 (1960).

Blasius et al., J. Chromatog, Vol. 11, pp. 84-92. (1963).

Primary E.\'aminerLeland A. Sebastian Attorney, Agent, or FirmLockwood,Dewey, Zickert & Alex [57] ABSTRACT This invention provides an absorbentcomposition comprising a reactant product of (l) amines or amides; (2)carbon disulfide, or carbonyl sulfide; (3) polyvalent metal ions; and,(4) a water-dispersable reactive polymeric material. A water-solublesilicate may be present as an optional material during the reaction. Thereaction is carried out in an alkaline water solution or dispersion, andthe above noted absorbent composition then precipitates.

12 Claims, No Drawings ABSORBENT COMPOSITION This is a continuation ofapplication Ser. No. 129,602, filed Mar. 30. 1971, now abandoned.

This invention relates to an absorbent composition, to a method for itspreparation, to novel compositions which can be made utilizing theabsorbent composition, and to novel methods of manufacturing azo dyes inthe presence of the novel absorbent composition.

It is an object of this invention to provide a novel substratecomposition. In this regard, an important object of the presentinvention is directed to the manufacture of a substrate compositionwhich can be used in the making of new and improved pigments which canbe either opaque or transparent.

It is a further object of this invention to provide a substrate which ishighly receptive to bonding with dyes and other colorants to form newand improved pigment compositions. It is an additional object of thisinvention to provide a substrate which can be present during thediazotization and/or coupling of azo dye intermediates to provide eitheran azo dye intermediate which can be used on a fabric, or the like, orto provide an azo dye pigment in which the azo dye is manufactured inthe presence of the substrate and remain on the substrate.

Materials used in the preparation of the composition of this inventionare (1) amines or amides; (2) carbon disulfide, or carbonyl sulfide; (3)a multi-valent metal ion; (4) a water-dispersable reactive polymericmaterial. A water-soluble silicate can be used as an optional material,and if present, has an effect on the particle size of the resultingabsorbent composition.

Examples of amines or amides that may be used in accordance with thisinvention include dicyandiamide; urea; thiourea; 2-alkyl imidazoline inwhich the alkyl group contains 2 to 22 carbon atoms, particularly such2-alkyl imidazolines which are also substituted in the first positionwith a hydroxyethyl group; the amides of fatty acids containing from 2to 18 carbon atom; ethoxylated amides of such fatty acids; aliphaticamines (primary, secondary, and tertiary, containing up to 20 carbonatoms); aliphatic diamines such as 1, 3 propylene diamine, N-tallow-l, 3propylene diamine; hydroxy amine such as 2-(2-amino ethoxy)ethanol,amino ethanolamine and monoethanolamine; aniline, toluidine andxylidene; cyclohexylamine and dicyclohexylamine l, 4-cyclohexanebis(methylamine); phenol diethanolamine; phenol ethanolamine and N-tolyldiethanolamine, and many others. For facilitating distribution in water,these amines are suitably used in the form of salts such as theacetates, diacetates, and the like.

The amount of amine or amide which is used in this invention is notcritical, but for most purposes an amount which is at least percent byweight, based on the weight of the polymer which is used.

The amount of carbon disulfide which is used in accordance with thisinvention is whatever amount is necessary to react with substantiallyall of the amine or am ides. In a preferred embodiment the carbondisulfide is added to the other reaction materials as an aqueous carbondisulfide emulsion. For facilitating the reaction of the carbondisulfide with the amines or amides I have found it convenient, and insome cases necessary (as disclosed hereinafter) to disperse or emulsifythe carbon disulfide extremely finely in water, using an emulsifyingagent such as water-soluble ethylene oxidereacted castor oil having ahydroxy] value of 88 and an HLB of 88 (e.g., Baker T.M. Surfactol 365).Suitably 10 parts by weight of this agent may be employed with partseach of water and equal volume of carbon disulfide with agitation toprovide a highly reactive suitable carbon disulfide-water emulsion foruse in accordance with this invention.

As indicated above the ratio of carbon disulfide to amino or amide issuitably somewhat in excess of that required for complete reaction ofall the amine or amide. Simple empirical tests will be describedhereinafter for the purpose of further explaining to those with ordinaryskill in the art the preferred amounts of carbon disulfide for use inconnection with a specific embodiment of the invention.

The water-dispersable reactive polymer compounds for use in accordancewith this invention to prepare the novel absorbent composition includecommercially available water-dispersable low molecular weight copolymersof styrene and maleic anhydrides (preferably molecular weight typicallyfrom 1600 to 2200) and other water-dispersable carboxyl polymericmaterials such as rosin acids and salts. It is preferred that thecarboxyl polymeric materials be selected from those high molecularweight materials or polymeric materials which have one or more aliphaticunsaturations therein, e.g., rosin acids, abeitic acid, maleic andacrylic polymers and copolymers, metal cross-linked acrylic copolymers,styrene copolymers, and the like. Also included within the classwater-dispersable reactive polymer compounds are water or ammoniacaldispersable expoxy, polyamide, polyester, cellulosic, e.g., alphacellulose, natural amino-containing proteinaceous materials such asgelatin, soya protein, casein, and the like. The amount of thewater-dispersable reactive resinous resin compound used in accordancewith this invention is not critical although it is preferred that theweight of the resin compound be greater than the combined weight of theamine compound and carbon disulfide. More preferably the amount of resincompound which is used is substantially greater then, e.g., 2-10 foldgreater than, the weight of the precipitated materials. Naturally, whenthe novel absorption material of this invention is produced in thepresence of a dye or dye intermediate, those embodiments utilizinggreater weight of water-dispersable reactive polymer materials willresult in pigments of relatively lower color value.

These water-dispersable or ammoniacal dispersable resin materials arewidely available commercially in the form of powders, and it ispreferred that this ingredient be added to the aqueous system, in themethod of manufacture of this invention, in the form of a relativelyfine powder.

The multi-valent metal ions which are provided in the method inaccordance with this invention can be selected to provide either opaqueor transparent substrates, as desired, in accordance with therequirements of the final product. Typically, these multi-valent metalions can include, for example, aluminum, zirconium, strontium, zinc,lead, molybdenum, tungsten, phosphomolybdate, barium, copper, cadmium,and other polyvalent ions.

When aluminum sulfate is added to the reaction system in aqueoussolution the resulting absorbent composition will be transparent. When asolution of a soluble barium salt is precipitated with a solution ofaluminum sulfate in the reacting medium of this invention, a

highly transparent substrate, containing a product known as blanc fixeis produced. However, if zinc chloride, zirconium oxychloride, leadnitrate, etc., are used the resulting substrate will be opaque.Furthermore when zirconium oxychloride, zinc chloride, lead nitrate,etc., are used, the resulting substrate composition is not capable ofbeing resolubilized in alcohol, etc. However when alumina hydrate isused the resulting substrate system is soluble in alcohols or amines andcan be resuspended in methylethylketone, acetone, propylene glycol,etc., for use in the manufacture of rotogravure ink, and the like. Also,essentially phosphorescent metal pigments utilizing zinc, copper cadmiumions, etc., in accordance with this invention, in conjunction with anyof the basic fluorescent dyes, UV absorber dyes, optical bleaching dyes,and the like provide a material which is highly useful as coatingcompositions in the manufacture of television screens, and the like. Itshould be emphasized, however, that the transparent pigments referred toabove are produced in a method utilizing alumina hydrate, and that ifaluminum silicate is added the resulting substrate will be opaque.

Some polyvalent metal ions are known to form inorganic gel polymersystems in water, e.g., alumina hydrate in water, and such polymericmaterials are contemplated to be equivalent to the reactive organicpolymeric materials referred to hereinbefore as illustrative of thatcategory of ingredients for use in accordance with this invention.Therefore, in some embodiments of this invention, some or all of thewater-dispersable reactive polymeric material can be supplied in theform of inorganic polymeric hydrates such as alumina hydrate,gel-forming clays, and other inorganic waterdispersable polymericmaterials.

The aqueous reaction solution is alkaline, and the metal polyvalent ionsare preferably added to such solution in the form of a slightlyacidified aqueous solution of the metal polyvalent ion. The preferredaqueous reaction solution of this invention is ammoniacal and theammonium hydroxide can provide some or most of the amine ingredientreferred to hereinbefore.

ln methods of manufacture of this invention, which will be furtherdescribed with the aid of the examples herein, substantiallyquantitative recover of organic solid materials is achieved. Thereactions are carried out in aqueous systems, and dyes or dyeintermediates can be added to the reaction system at any one of a numberof stages of the manufacture of the substrate of this invention. Forexample, in accordance with this invention, a color-free finely dividedsubstrate can be produced in an alkaline aqueous system from which thesubstrate is derived as a precipitate.

In an alternative embodiment of this invention, the polyvalent metalion, the water-dispersable reactive resin material, the amine compound,sodium silicate, are admixed and a dye or dye intermediate is also addedto this mixture, and a colored substrate of this invention isprecipitated after the addition of carbon disulfide and additionalpolyvalent metal ions.

In another alternative embodiment, the polyvalent metal ions, andwater-dispersable reactive resin material, the amine compounds, andcarbon disulfide are admixed in an alkaline aqueous system to provide anaqueous suspension of the fine color-free substrate of this invention,and a dye or dye intermediate can be added directly to the suspensionfor substantially complete absorption of the dye or dye intermediatethereon. On the other hand the color-free finely divided aqueoussuspension of the absorbent composition of this invention can beseparated from the aqueous reaction liquor, and the solids separated bydecantation, filtration. The solids can be washed in water. In anotheralternative embodiment of this invention the resulting separated,color-free, washed, finely divided solids can be resuspended and admixedwith dye or dye intermediate for complete absorption of the dye or dyeintermediate thereon.

The color-free separated solids of this invention are relatively heatstable and can be heated to temperatures at least as high as 400F,without disintegration or degradation and can be heated to temperaturesof about 300F for the purpose of drying the solids to provide asubstantially dry substrate. However, the colored substrate produced inaccordance with this invention can be used as aqueous-wet filter cake byadmixing with lipophylic vehicles and flushing the water therefrom usingconventional techniques such as, for example, by heating the resultingadmixture.

On the other hand, dry colored substrates in accordance with thisinvention are found to be surprisingly dispersable in lipophylicvehicles such as alkyd varnishes, nitro cellulose laquers, and the like.As indicated above, such admixtures produced from absorbent compositionsof this invention utilizing alumina hydrate produce transparent inks,whereas such compositions produced from embodiments of this inventionutilizing zirconium oxychloride in the aqueous reaction system produceopaque inks.

In the following examples all parts are expressed in parts by weight,and all percentages or percent (percent) are expressed in percent byweight based on the weight of the mixture, unless otherwise indicated,and all temperatures are expressed in degrees Fahrenheit. The followingexamples are provided for the purpose of illustration only, and it isnot intended that the invention be limited thereto. For example, otherreaction temperatures can be employed. Carbon disulfide is added atl00-l 10F in the examples, but can be added at lower temperature, or athigher temperature, provided the system is equipped to reflux vaporizedcarbon disulfide, or is pressurized, or otherwise equipped to retain thecarbon disulfide.

EXAMPLE 1 Tap water (4000 parts) and concentrated sodium silicatesolution (50 parts) are admixed and a small amount of silicone anti-foammaterial (T.M. Anti- Foam-60) is added thereto. The resulting sodiumsilicate solution is heated to 160F and a low molecular weight maleicanhydride-styrene copolymer (500 parts) is added with rpm high shearmixing. The maleic anhydride-styrene copolymer used in this example iscommercially available material (SMA 17352 A, T.M. Arco Chemical) whichis available in powder form. The molecular weight of the material is1590-1890, its acid number isabout 260', melting point l60l70F. Afterabout 25 minutes of mixing good dispersion is formed and 68 parts of26Baume ammonium hydroxide solution is added thereto. Mixing iscontinued for five minutes and an additional 68 parts of the ammoniumhydroxide solution are added and mixing is continued for 20 minutes. 100parts by weight of dicyandiamide is added to provide Mixture A.

Separately, a diamine N-Tallow propylene diamine diacetate, (T.M. Adogen570-A (100 parts) is melted. In this condition it has the appearance ofcoconut oil. This material is added when melted to Mixture A to producea mixture identified hereinafter as Mixture B. An aluminum sulfatesolution is separately prepared by dissolving 150 parts of aluminumsulfate with 1800 parts of water. A portion of the aluminum sulfatesolution (1000 parts) is added to the material identified as Mixture B,fairly slowly, and the resulting admixture is cooled to about l00F. Theresulting mixture is rather thick and upon continued stirring graduallybecomes somewhat less viscous, and is referred to hereinafter as MixtureC.

In a separate container 127 parts of carbon disulfide, 100 parts ofwater'(equal volumes), and parts of a surfactant (Surfactol 36 TL-3-30,T.M. Baker, which is castor oil-derived surfactant) is admixed andagitated to form a milky white emulsion.

The resulting emulsion is then added to Mixture C and an extremethickening occurs and new particles are formed. There is no odor ofcarbon disulfide at all coming from the resulting admixture. Theremaining 800 mils of the aluminum sulfate solution is now added andsubstrate solids form. The resulting admixture shall be referred tohereinafter as the substrate suspension.

EXAMPLE 2 The purpose of this example is to illustrate the production ofa colored substrate in accordance with this invention. Azosol BrilliantYellow parts) (8 GF), methyl cellosolve (300 parts) are admixed andheated to solubilized dye. The dye is an azo dye that is classified asanoil-soluble acid dye.

The resulting admixture referred to hereinafter as the dye solution ofExample 2, is admixed with the substrate suspension (3500 parts)referred to in Example 1. The color went onto the substrate immediatelyand when a portion of the colored material was added to filter paperthefiltrate was colorless showing complete bonding of the dye to thesubstrate, and no bleeding. Upon filtration and washing a dry pigmentpowder is produced without grinding upon drying at 300F.

EXAMPLE 3 The purpose of this example is to illustrate the use of thesubstrate produced by Example I with a basic dye. Rhodamine F3B is anextremely brillant dye. The Rhodamine dye (10 parts) and methylcellosolve (300 parts) are admixed and heated to approximately 100F tofacilitate solubilizing of the dye. The resulting solution of theRhodamine dye referred to hereinafter as the Rhodamine dye solution wasadmixed to substrate produced as in Example 1. lmediately upon admixing,color was imparted to the substrate, and when applied to filer paperthere was no bleed whatsoever through the filter paper.

EXAMPLE 4 The procedure of Example 1 is repeated, except that prior tothe addition of the carbon disulfide solution a dye solution produced inaccordance with Example 2 was added to the reaction mixture. Uponaddition of the carbon disulfide as in Example 1 thereto, the resultingsubstrate was colored, and evidenced no bleed upon being tested onfilter paper.

EXAMPLE 5 The procedure of Example 1 was repeated except thatimmediately prior to the addition of the carbon disulfide emulsion, theRhodamine dye solution of Example 3 was added thereto. Upon addition ofthe carbon disulfide emulsion a colored substrate was produced, and nobleed was observed when the substrate was tested on filter paper.

EXAMPLE 6 The purpose of this example is to illustrate the incorporationof a diazo type dye intermediate on the substrate of the invention, andthe subsequent coupling in the presence of the substrate to'producediazo dye colored substrate of this invention.

Water (4000 parts) is heated to 160F and concentrated sodium silicate(50 parts), a silicone emulsion anti-forming agent (5 parts) (GESilicone Anti-Foam and SMA resin (previously described in Example 1 (50parts) are admixed therewith and shear-blended thoroughly. Ammoniumhydroxide parts 26Be) is added and stirring is continued for about 25minutes for complete solubilization of the resin. To the resultingmixture dicyandiamide (20 parts) and Monazolene O (50 parts) are addedthereto. Monazolene O is a surface active l-hydroxyethyl2-alkylimidazoline in which the alkyl is an unsaturated 17 carbon chain.Paranitroaniline (200 parts) is added thereto and mixing is contined for10 additional minutes. The resulting mixture is referred to hereinafteras mixture 6-A.

An aluminum sulfate (iron-free) solution is prepared separately bydissolving parts of aluminum sulfate in 1800 parts of water at 120F. Tothis, 46 parts of sulfuric acid diluted with parts of water are added.The resulting admixture is referred to hereinafter as the aluminumsulfate solution.

A portion of the aluminum sulfate solution (1000 parts) is added to theMixture 6-A and the resulting admixture is cooled to l00F and the cooledsolution is referred to as 6-B hereinafter.

Carbon disulfide emulsion (237 parts) is prepared separately by admixing127 parts of carbon disulfide, 100 parts of water, and 10 parts ofSurfactol 36 T (L- 330, T.M. Baker, a castor oil-derived surfactant).The resulting emulsion is added to Mixture 6-B. Thereafter, anotherportion of the aluminum sulfate solution 1000 parts) is added to bringthe total volume to about 7000 parts by volume, and the entire volume istransferred to a larger container and cooled to 50F by addition of icethereto. The cooled solution is referred to hereinafter as Mixture 6-C.

The following solution is prepared for the diazotization of thesubstrate produced herein. To a solution of concentrated hydrochloricacid (358 parts) in 600 COUPLING 6-I Naphthol AS Supra(gaf) (100 parts)is pasted with methyl cellosolv or alcohol (150 parts). Sodium hydroxide(40 parts) dissolved in water (700 parts), the sodium hydroxide solutionis added to the naphthol solution and the resulting admixture is heatedto 180F. The resulting admixture forms a clear solution. The resultingadmixture is diluted with water to bring the weight of the batch toabout 1800 parts.

The resulting naphthol solution is added to a batch of diazo substrateproduced in accordance with this example, and mixed 30 minutes. Theresulting admixture is filtered and washed and filtered again to providea colored substrate which evidences no bleed in a filter paper test.

COUPLING 6-ll Methocellosolv (200 parts) is admixed with Monazoline(which was described earlier) (50 parts) and the resulting admixture isheated to 180F. The heated admixture is added to beta-naphthol (200parts) and a clear solution results. Water is added to the resultingsolution to bring the batch to 1800 parts, and this procedure was usedin accordance with the procedure of this example as described underCoupling 6-B.

EXAMPLE 7 The purpose of this example is to illustrate another use ofthe method of this invention to produce a colored substrate or pigment.To water at 120F (4000 parts) concentrated sodium silicate solution (100parts) and ammonium hydroxide solution (28C Be) (112 parts) andthoroughly mix. An ammoniadispersable resin which is commerciallyavailable under the trade name Pentalyn 261 (500 parts) is added theretoand mixed therein with high shear blending. This ammonia-dispersableresin is a high acid number, pale rosin-derived synthetic resin. It hasan acid number in the range 196-210, a softening point (drop method)l65-l75C and is available as a water white powder. It is noted thatabietic acid which is a major constituent of rosin acid is a complexhigh molecular weight acid having a carboxyl group and two aliphatictype unsaturations per molecule. The resulting admixture is heated to170F and Monazoline O (100 grams, which was described hereinbefore, isadmixed and stirred until fully dissolved.

When the previously added ingredients are fully dissolved Hiltacid Blueliquid (60 parts) is added thereto and mixed therewith for approximatelyminutes. The resulting admixture is cooled to a temperature in the rangel0OF-1 10F. A carbon disulfide emulsion (onehalf of the emulsionprepared as in Example 1), is added and allowed to react forapproximately 10 minutes.

The resulting admixture is referred to hereinafter as mixture 7-A.

In a separate container an aluminum sulfate solution is prepared byadmixing aluminum sulfate (75 parts) in water (200 parts) at 120C andadmixing therewith a dilute sulfuric acid solution prepared by dilutingconcentrated sulfuric acid (138 parts) with 525 parts of water.

To the mixture identified hereinbefore as solution 7-A the aluminumsolution is added over a period of about minutes, and the resultingmixture is heated to approximately 160F after that time. The resultingmixture is then cooled, decanted, and the recovered solids are washedand filtered.

EXAMPLE 8 The purpose of this example is to illustrate an alternativeembodiment for the production of a substrate in accordance with thisinvention which is particularly useful in connection with acid dyes.

To water at 140F (4000 parts), concentrated sodium silicate aqueoussolution parts) SMA resin (described hereinbefore) (500 parts) areadmixed and under high shear blend conditions for 5 minutes. An aqueousammonium hydroxide (26Be) parts) is added thereto and the high shearblending is continued until complete solution of the previously addedingredients is achieved. N-tallow l3 propyldiamine (commerciallyavailable as Adogen 570 A, T.M. Ashland Chemical Company) (100 parts) ismelted and added thereto. The resulting mixture is referred tohereinafter as Mixture 8-A.

A zirconium oxychloride solution is prepared by dissolving zirconiumoxychloride parts) in water (1800 parts) at 70F. A portion of thezirconium chloride solution (900 parts) is added to the mixturepreviously identified as Mixture 8-A and the resulting admixture iscooled to a temperature in the range lO0-1 10F. To the cooled solution acarbon disulfide emulsion (100 parts), prepared as described in Examplel, is added with stirring. No odor of carbon disulfide was detectedemanating from the mixture. The remaining portion of the zirconiumsolution (900 parts) is added with mixing. The resulting reactionmixture was permitted to settle, was decanted, and the recovered solidswere washed and filtered. The filter cake was divided into 4 parts andone of the parts was used as follows.

A zirconium chloride solution is prepared by dissolving zirconiumoxychloride (25 parts) in water 1800 parts) at 70F, and a fourth of thefilter cake produced in Example 8 hereinbefore was resuspended therein.Hiltacid Blue (30 parts) was added to the re sulting suspension and theresulting admixture was heated 170F. All of the dye was immediatelyabsorbed on the suspended solid substrate of this invention. No bleedingwas observed when a portion of the suspension was tested on filterpaper. The resulting suspension was cooled and the solids were permittedto settle. After decantation and washing the solids were recovered byfiltration.

EXAMPLE 9 The purpose of this example is to further illustrate the useof the solid substrates in accordance with this invention in theproduction of the substrate of this invention with Rhodamine dyes.

One-half of the filter cake produced in Example 8 is suspended in water(2000 parts) and the resulting suspension is heated to F. In a separatecontainer Rhodamine B (5 parts), Rhodamine 6 GDN (5 parts) and methylcellosolve (100 parts) is admixed to dissolve the dye. The resulting dyesolution is admixed with the heated substrate suspension at 160F.Immediately upon blending the dye is removed from the water anduniformly and completely absorbed on the suspended substrate solids. Theresulting mixture is thereafter permitted to settle, and afterdecantation. the solids are washed and filtered.

EXAMPLE This example illustrates the use of the absorbent composition ofthis invention to produce pigments. To water at 140F (4000 parts)aqueous sodium silicate (50 parts), SMA resin previously described (500parts), dicyandiamide 100 parts). aqueous ammonium hydroxide (26Be) (135parts), Monazoline O (50 parts), previously described are admixed andshear blended until the resin is dissolved. The resulting admixture isidentified hereinafter as Mixture 9-A.

In a separate container an aluminum sulfate solution is prepared bydissolving aluminum sulfate 150 parts) in water (1800 parts) at [40F Tothe resulting solution, glacial acetic acid (50 parts), diluted withwater (50 parts), is added.

A portion of the resulting aluminum sulfate solution (950 parts) isadded to the mixture identified hereinbefore as Mixture 9-A, and theresulting admixture is cooled to a temperature in the range 100110F. Tothe cooled solution carbon disulfide emulsion (100 parts), prepared asin Example 1, is added with stirring. No odor of carbon disulfide wasobserved emanating from the reaction mixture. The remaining portion ofthe aluminum sulfate solution (950 parts) was added and the resultingadmixture was permitted to stand for approximately 1/2 hour prior todecantation. The resulting collected solids were washed with water andfiltered.

The filter cake is divided into substantially two equal parts. The firsthalf of the filter cake is dispersed in water (2000 parts) at 140F and amixture made up from methyl cellosolve (300 parts) and Azosol Yellow 8GPparts) is added thereto. The dye solution, when added to the suspendedfilter cake is found to be immediately dispersed and immediately the dyeis observed to be absorbed on the suspended solids.

The other half of the filter cake is suspended in water (2000 parts) at140F. A dye solution prepared by admixing Rhodamine B (5 parts), andRhodamine 6GN (5 parts) in methyl cellosolve (200 parts) and heated tosolubility of dye. The resulting dye solution is filtered to removefines and is added to the suspended color filter cake. TheRhodamine-colored filter cake and the Azosol yellow filter cakedispersions are admixed and thoroughly dispersed, and filtered anddried.

EXAMPLE 1 l g The purpose of this example is to illustrate the use ofzinc chelate in the production of the absorbent composition of thisinvention. To water (4000 parts) at 140F, concentrated aqueous sodiumsilicate solution (50 parts), SMA resin (500 parts), aqueous ammoniumhydroxide (26Be) (135 parts) are added and shear blended to bring aboutsolubilization of the resin. To the resulting suspension dicyandiamide(100 parts), and N-tolyl 1-3 propyl diamine (50 parts) are added. Theresulting admixture is cooled to a temperature in the range l00-1 10F,and the cooled mixture is identified hereinafter as Mixture 1 l-A.

In a separate container a zinc solution is prepared by dissolving a zincchelate (80 parts) in water (1800 parts) at 140F. To the resultingchelate solution a mixture of glacial acetic acid (106 parts) and tapwater (100 parts) are admixed.

A portion of the resulting chelate solution 1000 parts) is added to themixture identified above as Mixture ll-A and the resulting admixture iscooled to a temperature l00-110F. A carbon disulfide emulsion 100 parts)is introduced at the bottom of the resulting reaction liquor and no odorof carbon disulfide was observed emanating therefrom. The remainingportion of the chelate solution (1000 parts) is added to the reactionmixture, and after approximately 20 minutes the solids were permitted tosettle, the supernatent liquid was decanted therefrom, the solids werewashed in watger, and recovered as a filter cake by filtration.

EXAMPLE 12 The purpose of this example is to illustrate the productionof a blaze red pigment. To water at 140F (4000 parts) aqueous sodiumsilicate (50 parts), Hiltamine Acetic White DML (20-1569) (2 parts),uvinal (DS-49) (2 parts) are added and shear blended for one minute; SMAresin (500 parts), an effective but small amount of an anti-foam (GE.Anti-Foam and aqueous ammonium hydroxide solution (26Be) (135 parts) areadmixed and shear blended 20-30 minutes until complete solubilization ofthe resin is achieved. To the resulting admixture dicyandiamide parts)and Monazoline 0 (50 parts) are admixed and the resulting mixture isstirred for approximately 5 minutes. The resulting mixture is identifiedhereinafter as Mixture 12-A. In a separate container an aluminum sulfatesolution is prepared by dissolving aluminum sulfate (150 parts) in water(1800 parts) at F. To this aluminum sulfate solution a sulfuric acidsolution, prepared by admixing concentrated sulfuric acid (92 parts)diluted in water (150 parts), is added at 60F.

A portion of the resulting aluminum sulfate solution (800 parts) isadded slowly to the mixture identified hereinbefore as Mixture 12-A toallow the pigment solids to form. After complete addition of the portionof aluminum sulfate a dye solution is added to the resulting mixture(identified hereinafter as Mixture 12-B).

The dye solution is prepared by dissolving Rhodamine 6 GDN (14 parts),Rhodamine B (14 parts) dissolved in methyl cellosolve (200 parts) and byheating the mixture to 150F. The dye solution is added to the mixtureidentified above as Mixture l2-B and the mixture is heated to 150F. Theresulting admixture is cooled to a temperature in the range 100110F anda carbon disulfide emulsion (100 parts), prepared as described inExample 1, is then added. The remainder of the aluminum sulfate solution1,200 parts) is added slowly in 200 part increments to the resultingadmixture. The solids are then separated by filtration.

The above procedure is repeated to provide a second filter cake exceptthat all of the dye ingredients are eliminated from the secondprocedure, and the resulting reaction mixtureis not filtered. A portionof the. re-

sulting second reaction mixture(3,000 parts) are a'd- EXAMPLE 13 Towater 4000 parts) at F, concentrated aqueous sodium silicate (50 parts),SMA resin (500 parts) described hereinbefore, aqueous ammonium hydroxide(26Be) 135 parts) are admixed and shear blended to wet-out the resin.The resulting mixture is identified hereinafter as Mixture l3-A. In aseparate container an aluminum sulfate solution is prepared by admixingaluminum sulfate 150 parts) with water 1600 parts) and to the resultingaluminum sulfate solution a diluted sulfuric acid is added. The dilutedsulfuric acid is prepared by diluting concentrated sulfuric acid (46parts) with water (175 parts).

A portion of the aluminum sulfate solution (400 parts) is added to themixture identified as Mixture l3-A, and dicyandiamide (100 parts)Monazoline (50 parts) an additional portion of the alulminum sulfatesolution (400 parts) is added. The resulting admixture is cooled to atemperature in the range 100-l F and carbon disulfide in emulsion (100parts), prepared as in Example 1, is added thereto, The remainder of thealuminum sulfate solution (800 parts) is added to the resultingadmixture. The suspension of finely divided solids is mixed thoroughlyand divided into two equal portions. One-half of the above batch ispermitted to settle, is washed, and filtered to become solids as afilter cake. The resulting filter cake is resuspended in water (120F)(2000 parts) and Rhodamine 6GDN- 6018 BAGF (30 parts) is added theretoto form a Rhodamine colored suspension.

To the other half of the batch a dye solution is added. The dye solutionis prepared by dissolving Azosol Yellow 8 GF parts) in methyl cellosolve(200 parts). The Rhodamine-colored suspension and the A2050] Yellowsuspension are then admixed to produce blaze orange, in accordance withthis invention.

EXAMPLE 14 To water (4000 parts) heated to 160F, Pentalyn 261 resin (500parts), aqueous ammonium hydroxide (26Be) 156 parts) are admixed underhigh shear conditions. This resulting mixture is referred to hereinafteras Mixture 14-A.

In a separate container Monazoline 0 100 parts), cyclohexylamine 100parts), methyl cellosolve 100 parts), and beta-naphthol (400 parts) arethoroughly admixed until a substantially homogeneous dispersion isachieved. The resulting homogeneous dispersion is admixed with themixture referred to above as Mixture l4-A.

The resulting admixture is referred to as Mixture l4-B.

In another container an aluminum sulfate solution is prepared bydissolving 150 parts of aluminum sulfate in 1800 parts of water at 120F.To this solution, a dilute sulfuric acid is prepared by dissolving 46parts of concentrated sulfuric acid in 175 parts of water at 70F. Aportion of the aluminum sulfate solution (900 parts) is added to themixture identified above as Mixture l4-B. Carbon disulfide emulsion (300parts) prepared as in Example 1 is then admixed with the solution andfinally the balance of the aluminum sulfate solution is added thereto.Substantially quantitative recovery of the organic materials wasachieved as finely divided settled solids. The resulting dispersion waspermitted to settle, the supernatent liquid was decanted, and the solidswere washed with water and resuspended in water (6000 parts). In aseparate container concentrated hydrochloric acid (300 parts) isdissolved in water (3000 parts) and the acid solution is cooled to about50F by addition of ice thereto. In a separate container paranitroaniline(200 parts), sodium nitrite parts), and water (400 parts) are admixedand heated to 180F. A paste is formed and the resulting paste is addedto the cooled hydrochloric acid referred to above and the temperature ismaintained at approximately 50F by addition of ice, if necessary, Itwill be apparent to those of ordinary skill in the dying art that theparanitroaniline is being diazotized and the diazotization reagents andconditions are conventional. After the diazotization is complete theinorganic acid is neutralized by addition thereto of a solution preparedby dissolving sodium acetate grams) in water at 120F (500 parts) andsubsequent addition thereto of glacial acetic acid (50 parts). Thediazotizing solution is neutralized to congo red neutral. The resultingneutralized solution is referred to as the coupling solution.

Cotton fabric is drawn through the naphthol solution of this example andexcess liquid is wrung therefrom. The thus treated fabric is then passedthrough the diazo solution and the red color is instantly developed. Ithas been found that the procedure of this example is eminentlysatisfactory for use in dyeing or printing on, any textile fabricincluding cotton, nylon, wool, silk, etc. It should be emphasized thatthe diazotizing and coupling reactions which are used in accordance withthis invention utilize entirely conventional diazotizing and couplingconditions, and diazotizing and coupling of the intermediate presentwith or absorbed on the substrate of this invention appears to takeplace at an accelerated rate. It has been found that any of the azo dyeintermediates can be diazotized and coupled with any of the naphthol oramine azo dye intermediates which are well known and conventionallyused, and that no special accomodation is necessary because of thepresence of the substrate of this invention during the diazotizing orcoupling.

EXAMPLE 15 The procedure of Example 1 is repeated, except that dissolvedlead nitrate is substituted for a portion of the aluminum sulfate. Theresulting washed substrate is then admixed with a chromate solution andcolor is immediately developed on the substrate.

EXAMPLE 16 To water (4000 parts) at 160F a concentrated aqueous solutionof sodium silicate (50 parts), a small amount of anit-foam agent (T.M.,G.E. Anti-Foam 60) and a rosinderived ammonia-dispersable resin referredto previously as pentalyn 269 (500 parts) are mixed and thoroughly shearblended. Ammonium hydroxide solution (26Be) parts) is admixed andstirred until complete resin solubility is achieved. Paranitroanilineparts) is then added and the mixture is stirred for approximately 10minutes.

An aluminum sulfate solution is prepared in accordance with theprocedure described in Example 6 herein. A portion of the aluminumsulfate solution 1000 parts) is then admixed with the reaction mixtureand the entire reaction mixture is cooled to a temperature in the rangel001 10F. A carbon disulfide emulsion prepared in accordance with theprocedure described in Example 1 herein (200 parts) is added. Thereaction of carbon disulfide in the procedure of the present exampletook approximately 45 minutes. Thus,

in the present example. the take-up of the carbon disulfide isrelatively slow. The remaining portiton of the aluminum sulfate solution(1000 parts) is then admixed therewith, and from this point theprocedure followed is identical to the procedure of Example 6 includingthe diazotizing, and coupling reaction, except that 300 parts ofbeta-naphthol were used in the coupling reaction of the present example.A finely divided nonbleeding, excellent para-red pigment was produced.

In each of the examples referred to hereinbefore the organic ingredientsare substantially quantitatively recovered in the solid substrate.

This invention therefore provides a new method of making diazo dyepigments either by absorbing the coupled dye on the substrate, addingand absorbing either the diazo or naphthol amine moieties on thesubstrate by addition of the respective moiety to the reactioningredient in the method of this invention, by addition of thesemoieties to an uncolored substrate, or by diazotizing the azointermediate in the presence of the substrate either after thesubstrateis recovered, or while the substrate is still in the reaction liquor.Furthermore, as illustrated by the above examples, coupling of azo dyeintermediates which are respectively absorbed on separate substrates ofthis invention, and admixing these substrates produces an extremelyrapid coupling reaction. As indicated above it has been found that for agiven amount of azo dye intermediate, the resulting pigment, when madein the presence of the substrate of this invention, has a higher colorvalue than the color value which would have been achieved from the sameamount of intermediate used to manufacture the dye separately prior toabsorption on a color-free substrate of this invention or on othersubstrates.

When tertiary amines or amides are utilized as ingredients to providethe amine or amide, it is essential that the carbon disulfide beprovided in the reaction system as an emulsified carbon disulfide inorder to achieve the desired reaction.

To assist one with ordinary skill in the art to practice the inventionin its broadest aspects, the following general principles areapplicable. As indicated above, it is preferred that the weight of thepolymeric material be a major portion of the reaction ingredients. Theamount of carbon disulfide which is utilized depends on the amount ofamine and other reactive groups which are available in the mixture. Todetermine a preferred amount of carbon disulfide for use in accordancewith the preferred method of this invention, particular amounts ofrespective selected ingredients from the respective ingredient groupsreferred to above are admixed, for example, following the generalprocedure of Example 1, up to the step at which carbon disulfide isadded. At that point incremental quantities of carbon disulfide areadded (preferably as an aqueous emulsion) while the reaction mixture ismaintained at a temperature in the range l-l F. The incremental additionis continued until an odor of carbon disulfide is detectable emanatingtherefrom.

A record is made of the total amount of carbon disulfide added, and forthe purposes of the preferred embodiment of this invention, an amount ofcarbon disulfide which is between 90 and 1 10 percent of that totalamount of carbon disulfide is the preferred amount. The mixture isheated to lF in order to remove any excess, unreacted carbon disulfide.

As indicated above, the polyvalent metal salts are added inwater-soluble form, preferably in slightly acidic solutions, and theamount of salt which is added is at least that amount which is necessaryto bring about complete precipitation of the substrate of thisinvention. The amount is not critical, however. An insufficient amountwill result in less than quantitative recover of product, and copiousexcesses of polyvalent metal salts can be added without detrimentaleffect. It is to be understood, of course, that metals which are knwonto be antagonistic to a particular dye should not be used in themanufacture of substrates which are intended for use with thatparticular dye.

This invention provides a substrate which exhibits extremely efficientfixing of colorants, colorant intermediates, optical brighteners,ultra-violet absorbers, and the like. By fixing is means absorption orbonding whether physical or chemical with the result that the fixedmaterial is substantially removed from a medium, and is substantiallyadhered to the substrate. Ultraviolet light inhibitors or absorberswhich are absorbed on the substrate of the present invention include thebenzophenones, benzotriazols, silicates, and others including resorcinolmonobenzoate, hexamethylphosphoric triamide, substituted acrylonitriles,and metal organic complexes. For example, 4-methoxy-2-hydroxybenzophenone, 4-octyloxy-2- hydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone,

4-methoxy-2,2-dihydroxybenzophenone, 4-octyloxy-2,2-dihydroxybenzophenone, 4-methoxy-2-hydroxy-5- sulfonic acid,sodium-4,4'-dimethoxy-2,2-dimethoxy- 5-sulfo-benzophenone, 2( 2hydroxy-5-methylphenyl benzotriazole, alkylated (2'-hydroxy-5'-phenyl)benzotriazoles, phenyl salicylate, 4-5-butylphenyl salicylate,p-octylphenyl salicylate.

Fluorescent whitening agents and brighteners are also efficiently fixedon the substrate of the present invention. For example, the stilbenederivatives and equivalent materials conventionally used for thispurpose and well known to those skilled in this art are efficientlyfixed.

While in the foregoing specification various embodiments of the presentinvention have been described, it will be apparent to those skilled inthis art that modifications and variations therefrom may be made withoutdeparting from the spirit and scope of this invention. Accordingly, thesubject invention is to be limited only by the scope of the appendedclaims.

I claim:

1. An absorbent composition comprisng an effective amount of thereaction product formed in an alkaline aqueous medium of polyvalentmetal ions, amine or amide compound, carbon disulfide, and a majoramount of water-dispersible or ammoniacal-dispersible reactive highmolecular weight compound or polymer material, wherein the amount ofcarbon disulfide is sufficient to react with substantially all of theamine or amide.

2. The reaction product of claim 1 wherein the waterdispersible orammoniacal-dispersible reactive high molecular weight compound orpolymer material is selected from the group consisting of polymers ofunsaturated carboxylic acid, epoxy, polyamide, alpha cellulose,polyester, soya protein, gelatin, casein, and mixtures thereof.

3. The absorbent composition of claim 1 wherein the amine compounds arealkanol amines.

4. The composition of claim 1 in which the amine or amide compound isselected from the group which includes dicyandiamide; urea; thiourea;2-alkyl imidazoline in which the alkyl group contains 222 carbon atoms;2-alkyl imidazolines in which the alkyl substituent has 222 carbonatoms, and which is also substituted in the 1 position with hydroxyethyl group; amides of fatty acids having 2-20 carbon atoms; primary,secondary and tertiary aliphatic amines having 8A8 carbon atoms;aliphatic diamines; l, 3-propylene diamine; N-tallow-l 3 propylenediamine; hydroxy amines; 2-(2-amino ethoxy)ethanol, amino ethanolamineand monethanolamine; aniline, toluidine and xylidene; cyclohexylamineand dicyclohexylamine; phenol diethanolamine; phenol ethylethanolamine,and N-tolyl diethanolamine, and mixtures thereof.

5. The reaction product of claim 1 wherein the product is produced in areaction system in which the carbon disulfide is added as an emulsion inwater.

6. The absorbent composition of claim 1 in which the water-dispersibleor ammoniacal-dispersible reactive high molecular weight compound orpolymer material is selected from the group consisting of aliphaticunsaturated carboxylic acids having at least one carboxyl group permolecule and two or more unsaturations per molecule, and polymers ofcompounds having two or more carboxyl groups per molecule and at leastone aliphatic unsaturation per molecule.

7. An absorbent composition comprising an effective amount of thereaction product formed in an alkaline aqueous medium of polyvalentmetal ions, amine or amide compound, carbon disulfide, and a majoramount of water-dispersible copolymer of styrene and maleic anhydride,wherein the weight of the waterdispersible copolymer is greater than thecombined weight of the amine or amide compound and carbon disulfide, andwherein said amine or amide compound is used in an amount sufficient toprovide at least 5 percent by weight based on the weight of thecopolymer used, and in which the carbon disulfide is used in an amountsufficient to react with substantially all of said amine or amide.

8. The absorbent composition of claim 7 wherein the water-dispersiblereactive polymeric material is selected from the group consisting of lowmolecular weight copolymers of styrene and maleic anhydrides.

9. The absorbent composition of claim 8 wherein said copolymers have amolecular weight from 1600 to 2200.

10. The absorbent composition of claim 7 wherein said product is formedin said alkaline aqueous medium by first admixing said polyvalent metalions, said amine or amide compound, and said major amount of copolymersof styrene and maleic anhydride, and thereafter admixing said carbondisulfide in an amount sufficient to react with substantially all ofsaid amine or amide.

11. The absorbent composition of claim 10 wherein a water solublesilicate is also present in said aqueous alkaline medium.

12. An absorbent composition comprising an effective amount of thereaction product formed in an alkaline aqueous medium by first admixingpolyvalent metal ions amine or amide compound, and a major amount ofwater-dispersible copolymer of styrene and maleic anhydride, andadmixing carbon disulfide with the preceding ingredients at atemperature in the range l 10F., wherein the amount of water-dispersiblecopolymer is greater than the combined weight of said amine or amide andcarbon disulfide, wherein the amount of said amine or amide is at least5 percent based on the weight of the copolymer, and wherein the amountof carbon disulfide is sufficient to react with substantially all of theamine or amide.

DATED Column Column Column Column Column Column Column Column ColumnColumn Column Column Column Column Column Column Column UNITED STATESPATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION 3,883,438 May 13,1975 Robert K. Remer PATENT NO.

lN\/ ENTOR(S) I [SEAL] It is cerfified that error appears in theabove-identified patent and thatsaid Letters Patent are hereby correctedas shown below:

3, line 62, "and" should read the 4, lines 34 and 35 "(percent) shouldread 5, line 1, "N-Tallow" should read Ntallow- 5, line 2, after"Adogen" insert 6, line 20, "anti-forming" should read antifoaming- 6,line 23, "Be" should read -Be' 7, line 33, "Be" should read -Be'- 7,line 62, "200" should read -2000 7, line 62, "120C" should read -l20F--8, line 14, "Be" should read Be- 9, line 10, "Be" should read -Be'- 9,line 56, "Be" should read Be'- 10, line 22, "Be" should read -Be' 11,line 3, "Be" should read Be'- 11, line 39, "Be" should read -Be'- 12,line 52, "mixed" should read admixed- 12, line 54, "Be" should read Be'Sugned and Sealed this seventeenth Day Of February 1976 Attest:

RUTH C. MASON Arresting Officer DATED Column Column Column Column ColumnColumn Column Column Column Column Column Column Column Column ColumnColumn Column [SEAL] UNITED STATES PATENT AND TRADEMARK OFFICECERTIFICATE OF CORRECTION 3,883,438 May 13, 1975 Robert K. Remer PATENTNO.

NVENTOR(S) It is certtfied that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

line

"and" should read the lines 34 and 35 (percent) should read l,"N-Tallow" should read Ntallow- 2, after "Adogen" insert line line lineline line line line line line line line line line line line Signed andScaled this seventeenth D ay Of February 1 976 Arrest:

RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner ofPate/11s and Trademarks

1. AN ABSORBENT COMPOSITION COMPRISING AN EFFECTIVE AMOUNT OF THEREACTION PRODUCT FORMED IN AN ALKALINE AQUEOUS MEDIUM OF POLYVALENTMETAL IONS, AMINE OR AMIDE COMPOUND, CARBON DISULFIDE, AND A MAJORAMOUNT OF WATER-DISPERSIBLE OR AMMONIACAL-DISPERSIBLE REACTIVE HIGHMOLECULAR WEIGHT COMPOUND OR POLYMER MATERIAL, WHEREIN THE AMOUNT OFCARBON DISULFIDE IS SUFFICIENT TO REACT WITH SUBSTANTIALLY ALL OF THEAMINE OR AMIDE.
 2. The reaction product of claim 1 wherein thewater-dispersible or ammoniacal-dispersible reactive high molecularweight compound or polymer material is selected from the groupconsisting of polymers of unsaturated carboxylic acid, epoxy, polyamide,alpha cellulose, polyester, soya protein, gelatin, casein, and mixturesthereof.
 3. The absorbent composition of claim 1 wherein the aminecompounds are alkanol amines.
 4. The composition of claim 1 in which theamine or amide compound is selected from the group which includesdicyandiamide; urea; thiourea; 2-alkyl imidazoline in which the alkylgroup contains 2-22 carbon atoms; 2-alkyl imidazolines in which thealkyl substituent has 2-22 carbon atoms, and which is also substitutedin the 1 positioN with hydroxy ethyl group; amides of fatty acids having2-20 carbon atoms; primary, secondary and tertiary aliphatic amineshaving 8-18 carbon atoms; aliphatic diamines; 1, 3-propylene diamine;N-tallow-1, 3 propylene diamine; hydroxy amines; 2-(2-aminoethoxy)ethanol, amino ethanolamine and monethanolamine; aniline,toluidine and xylidene; cyclohexylamine and dicyclohexylamine; phenoldiethanolamine; phenol ethylethanolamine, and N-tolyl diethanolamine,and mixtures thereof.
 5. The reaction product of claim 1 wherein theproduct is produced in a reaction system in which the carbon disulfideis added as an emulsion in water.
 6. The absorbent composition of claim1 in which the water-dispersible or ammoniacal-dispersible reactive highmolecular weight compound or polymer material is selected from the groupconsisting of aliphatic unsaturated carboxylic acids having at least onecarboxyl group per molecule and two or more unsaturations per molecule,and polymers of compounds having two or more carboxyl groups permolecule and at least one aliphatic unsaturation per molecule.
 7. Anabsorbent composition comprising an effective amount of the reactionproduct formed in an alkaline aqueous medium of polyvalent metal ions,amine or amide compound, carbon disulfide, and a major amount ofwater-dispersible copolymer of styrene and maleic anhydride, wherein theweight of the water-dispersible copolymer is greater than the combinedweight of the amine or amide compound and carbon disulfide, and whereinsaid amine or amide compound is used in an amount sufficient to provideat least 5 percent by weight based on the weight of the copolymer used,and in which the carbon disulfide is used in an amount sufficient toreact with substantially all of said amine or amide.
 8. The absorbentcomposition of claim 7 wherein the water-dispersible reactive polymericmaterial is selected from the group consisting of low molecular weightcopolymers of styrene and maleic anhydrides.
 9. The absorbentcomposition of claim 8 wherein said copolymers have a molecular weightfrom 1600 to
 2200. 10. The absorbent composition of claim 7 wherein saidproduct is formed in said alkaline aqueous medium by first admixing saidpolyvalent metal ions, said amine or amide compound, and said majoramount of copolymers of styrene and maleic anhydride, and thereafteradmixing said carbon disulfide in an amount sufficient to react withsubstantially all of said amine or amide.
 11. The absorbent compositionof claim 10 wherein a water soluble silicate is also present in saidaqueous alkaline medium.
 12. An absorbent composition comprising aneffective amount of the reaction product formed in an alkaline aqueousmedium by first admixing polyvalent metal ions, amine or amide compound,and a major amount of water-dispersible copolymer of styrene and maleicanhydride, and admixing carbon disulfide with the preceding ingredientsat a temperature in the range 100*-110*F., wherein the amount ofwater-dispersible copolymer is greater than the combined weight of saidamine or amide and carbon disulfide, wherein the amount of said amine oramide is at least 5 percent based on the weight of the copolymer, andwherein the amount of carbon disulfide is sufficient to react withsubstantially all of the amine or amide.